JP6584410B2 - Improved adsorption of acid gases - Google Patents
Improved adsorption of acid gases Download PDFInfo
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- JP6584410B2 JP6584410B2 JP2016541396A JP2016541396A JP6584410B2 JP 6584410 B2 JP6584410 B2 JP 6584410B2 JP 2016541396 A JP2016541396 A JP 2016541396A JP 2016541396 A JP2016541396 A JP 2016541396A JP 6584410 B2 JP6584410 B2 JP 6584410B2
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/025—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with wetted adsorbents; Chromatography
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- C10K1/00—Purifying combustible gases containing carbon monoxide
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- C10K1/00—Purifying combustible gases containing carbon monoxide
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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Description
発明の属する技術分野
本発明は、酸性ガスのアルミナ吸着剤上への選択的な吸着による、液体又はガス流からの酸性ガスの除去に関する。
The present invention relates to the removal of acidic gas from a liquid or gas stream by selective adsorption of acidic gas onto an alumina adsorbent.
発明の背景
酸性ガスは、COS及びH2Sなどのこれらのガスの幾つかが硫黄源であり、従って潜在的大気汚染物質であるために、例えば、石油炭化水素などの材料における望ましくない不純物である。COS及びH2Sはまた、汚染物質が、プロピレンなどの石油由来の重合性オレフィン中に存在する場合、例えば、重合触媒の被毒により、工業プロセスの望ましくない汚染物質としても作用する。酸性ガスは、原料中に最初に存在する、汚染物質としてかかるプロセスに導入され得るか、又はそれらは、二酸化炭素と硫化水素又は他の硫黄化合物との分子篩い触媒による反応の結果として、処理工程で形成され得る。例えば、酸性ガスは、天然ガス流に見出すことができ、汚染物質であることに加えて、COS、H2S、CO2、CS2、SO2、HCl、HF及びHBrなどの酸性ガスは、天然ガスパイプライン、パイプライン設備、及び他の化学処理装置を腐食し得る。
BACKGROUND OF THE INVENTION Acid gases are undesirable impurities in materials such as petroleum hydrocarbons because some of these gases such as COS and H 2 S are sulfur sources and thus potential air pollutants. is there. COS and H 2 S also act as undesirable pollutants in industrial processes when the pollutants are present in petroleum-derived polymerizable olefins such as propylene, for example, due to poisoning of the polymerization catalyst. Acid gases may be introduced into such processes as pollutants that are initially present in the feed or they may be processed as a result of molecular sieve catalyzed reaction of carbon dioxide with hydrogen sulfide or other sulfur compounds. Can be formed. For example, acid gases can be found in natural gas streams, and in addition to being pollutants, acid gases such as COS, H 2 S, CO 2 , CS 2 , SO 2 , HCl, HF and HBr are It can corrode natural gas pipelines, pipeline equipment, and other chemical processing equipment.
プロセス及び生成物の必要な純度に応じて、出発物質中のCOS濃度が、1重量百万分率(ppmw)未満に低下し、場合により100重量十億分率(ppbw)未満のレベルに低下することが必要となり得る。数ppmwの範囲内のCOSの濃度は、COSの沸点がプロピレンと3.4℃しか異ならないので、分別蒸留によりプロピレンなどの石油原料から効率的に分離することができない。 Depending on the required purity of the process and product, the COS concentration in the starting material is reduced to less than 1 parts per million (ppmw) and possibly to a level of less than 100 parts per billion (ppbw). It may be necessary to do. The concentration of COS within a range of several ppmw cannot be efficiently separated from petroleum raw materials such as propylene by fractional distillation because the boiling point of COS differs from propylene only by 3.4 ° C.
Khelghatianの米国特許第3,315,003号明細書は、H2S及びCO2並びにCOSの一部などの酸性ガスを除去するために、まず、炭化水素をスクラブするモノエタノールアミンなどの液体と炭化水素とを接触させることにより、炭化水素からCOSを除去する方法を教示している。炭化水素は、その後、蒸留される。それに続く幾つかの蒸留後、液体の底部生成物を、ソーダ石灰で処理して全ての残っているCOSを除去する。 Khelghatian U.S. Pat. No. 3,315,003 describes a liquid such as monoethanolamine that scrubs hydrocarbons first to remove acidic gases such as H 2 S and CO 2 and a portion of COS. It teaches a method for removing COS from hydrocarbons by contacting the hydrocarbons. The hydrocarbon is then distilled. After several subsequent distillations, the liquid bottom product is treated with soda lime to remove any remaining COS.
しかしながら、蒸留を含むプロセスによるCOSの分離は、更に、実質的に全ての液体を気化するためのエネルギーのコストのために非常に高価である。従って、有機液体からCOS不純物を除去するための他の手段を提供することが望ましい。 However, the separation of COS by processes involving distillation is also very expensive due to the cost of energy to vaporize substantially all of the liquid. Accordingly, it is desirable to provide other means for removing COS impurities from organic liquids.
また、例えば、触媒としてアルミナを用いて、H2Sを形成するために触媒的加水分解により炭化水素からCOSを除去することも提案されている。Frevelらの米国特許第3,265,757号明細書は、液体炭化水素と水との混合物を、20〜50℃の温度で、0.15質量%〜3質量%のナトリウム又はカリウムを含有する高表面積のアルカリ性の活性アルミナと接触させることによる液体炭化水素中に含まれるCOSの加水分解を教示している。特許権者らは、しかしながら、アルミナが完全乾燥している場合には加水分解反応は開始しないだろうと述べている。彼らは、反応前にイオンを含まない水を用いてアルミナ触媒を湿潤させること又は十分な量の水がアルミナ上に蓄積して加水分解反応の進行を可能にするまで、イオンを含まない水と液体炭化水素の混合物を触媒床に通すことのいずれかを示唆している。しかしながら、このプロセスが(これをH2Sに変換することにより)COSを除去する一方で、炭化水素から硫黄を除去しないが、別のプロセス工程により炭化水素からその後に更に除去されなければならない硫黄化合物の形を変更しているに過ぎない。 It has also been proposed to remove COS from hydrocarbons by catalytic hydrolysis, for example, using alumina as a catalyst to form H 2 S. U.S. Pat. No. 3,265,757 to Frevel et al. Contains a mixture of liquid hydrocarbon and water containing 0.15 wt% to 3 wt% sodium or potassium at a temperature of 20 to 50 ° C. It teaches the hydrolysis of COS contained in liquid hydrocarbons by contact with high surface area alkaline activated alumina. The patent holders, however, state that the hydrolysis reaction will not start if the alumina is completely dry. They use ion-free water to wet the alumina catalyst prior to the reaction, or until a sufficient amount of water accumulates on the alumina to allow the hydrolysis reaction to proceed. One suggests passing a mixture of liquid hydrocarbons through the catalyst bed. However, while this process removes COS (by converting it to H 2 S), it does not remove sulfur from the hydrocarbon, but sulfur that must be further removed from the hydrocarbon later by another process step. It only changes the form of the compound.
同じタイプの反応を扱う後の特許では、Polleckらの米国特許第4,491,516号明細書は、COSに対する水の比が1モルのCOS当たり1〜10モルの水、好ましくは1モルのCOS当たり1.5〜6モルの水の範囲であるか、又は約30%の炭化水素の飽和である場合、どちらの上限がより少ない量の水を提供しても、アルミナ上での水によるCOSの加水分解の反応速度を大幅に増加させ得ることを教示している。 In a later patent dealing with the same type of reaction, US Pat. No. 4,491,516 to Polleck et al. States that the ratio of water to COS is 1 to 10 moles of water, preferably 1 mole of water per mole of COS. If the range is from 1.5 to 6 moles of water per COS, or about 30% hydrocarbon saturation, whichever upper limit provides a smaller amount of water, it will depend on the water on the alumina. It teaches that the reaction rate of COS hydrolysis can be significantly increased.
Brownellらの米国特許第4,455,446号明細書は、アルミナ上で白金硫化物を含む触媒を用いる加水分解によるプロピレンからのCOSの除去を教示している。特許権者は、加水分解反応が、液相の場合に使用される35℃〜65℃の温度を有する気相又は液相のいずれかで実施され得ることを述べている。水の量は、加水分解されるべきCOSの化学量論量の少なくとも2倍も存在しなければならない。 U.S. Pat. No. 4,455,446 to Brownell et al. Teaches the removal of COS from propylene by hydrolysis using a catalyst containing platinum sulfide on alumina. The patentee states that the hydrolysis reaction can be carried out either in the gas phase or in the liquid phase having a temperature of 35 ° C. to 65 ° C. used in the liquid phase. The amount of water must be present at least twice the stoichiometric amount of COS to be hydrolyzed.
Harrisらの米国特許第4,391,677号明細書は、H2S、COS、及びCH3SHなどの硫黄不純物を含むブテン−1富化原料を脱硫するための方法を記載している。この方法は、供給流を、脱硫条件下で維持される脱硫領域に通し、且つH2S、COS、及びCH3SHを吸着、吸収、又はこれらを高沸点硫黄化合物に変換することが可能な少なくとも1つの脱硫媒体の電荷を含有することを含む。ここで実質的にH2S、COS、及びCH3SHを含まない、このように処理された供給流を、次に蒸留領域に通し、そして高沸点硫黄化合物を含有するブテン−2富化流として塔底生成物として回収される。脱硫領域は、活性アルミナの床に続いて酸化亜鉛の床を含む。活性アルミナは、20〜1000ppmの水の存在下でCOSをH2Sに加水分解し、H2S及びメチルメルカプタンを部分的に除去すると言われている。酸化亜鉛は、アルミナ床によって除去されていない全てのH2S及びメチルメルカプタンを除去すると言われている。 US Pat. No. 4,391,677 to Harris et al. Describes a process for desulfurizing butene-1 enriched feedstocks containing sulfur impurities such as H 2 S, COS, and CH 3 SH. This method allows the feed stream to pass through a desulfurization zone maintained under desulfurization conditions and to adsorb, absorb or convert H 2 S, COS, and CH 3 SH to high boiling sulfur compounds. Containing the charge of at least one desulfurization medium. A butene-2 enriched stream, wherein the feed stream thus treated, substantially free of H 2 S, COS, and CH 3 SH, is then passed through a distillation zone and contains high-boiling sulfur compounds. As a bottom product. The desulfurization zone includes a bed of zinc oxide followed by a bed of activated alumina. Activated alumina is said to hydrolyze COS to H 2 S in the presence of 20 to 1000 ppm of water, partially removing H 2 S and methyl mercaptan. Zinc oxide is said to remove all H 2 S and methyl mercaptan that have not been removed by the alumina bed.
COSはまた、ゼオライトの吸着剤上への吸着により液体炭化水素から除去されていた。Collinsの米国特許第3,654,144号明細書は、20当量パーセント〜約100当量パーセントの程度まで、アルカリ土類金属カチオン、好ましくはカルシウムカチオンとイオン交換されたアルカリ金属カチオンの形のゼオライトAを含む特定の修飾されたゼオライトA上でそれを吸着することによってCOSを除去することを開示している。 COS has also been removed from the liquid hydrocarbon by adsorption of zeolite onto the adsorbent. Collins U.S. Pat. No. 3,654,144 describes zeolite A in the form of alkali metal cations ion exchanged with alkaline earth metal cations, preferably calcium cations, to the extent of 20 equivalent percent to about 100 equivalent percent. To remove COS by adsorbing it on a specific modified zeolite A containing
Innesの米国特許第4,098,684号明細書は、それぞれ、13Xの分子篩い、及び4オングストロームの細孔径を有するゼオライトA篩いを含むゼオライトの二重床にCOS及び他の硫黄化合物を通すことによるそれらの除去を記載している。市販の13Xゼオライトは、存在する全てのH2S及びメルカプタンを除去すると言われている。13Xの篩いによるCOS吸着能力は小さいと言われている。13Xのゼオライトは、細孔開口部を介してアクセス可能な相互に結合した結晶内空隙を有する三次元的網目構造として記載されており、10オングストロームまでの限界寸法を有し且つ一般化学式:0.83±0.05 Na2O/1.00 Al2O3/2.48±0.038 SiO2を有する分子を認める。分子篩い床は、熱く、ほぼ非吸着性のパージガスを、約177℃〜316℃の温度で床に通すことによって再生され得る。 Innes U.S. Pat. No. 4,098,684 passes COS and other sulfur compounds through a double bed of zeolite containing a 13X molecular sieve and a zeolite A sieve having a pore size of 4 Angstroms, respectively. Describes their removal by. Commercial 13X zeolite is said to remove any H 2 S and mercaptans that are present. It is said that the COS adsorption capacity by 13X sieve is small. 13X zeolite is described as a three-dimensional network structure with interconnected intracrystalline voids accessible through pore openings, has a critical dimension of up to 10 angstroms, and a general chemical formula: A molecule having 83 ± 0.05 Na 2 O / 1.00 Al 2 O 3 /2.48±0.038 SiO 2 is observed. The molecular sieve bed can be regenerated by passing a hot, nearly non-adsorbing purge gas through the bed at a temperature of about 177 ° C to 316 ° C.
ゼオライト材料は、液体炭化水素からCOSなどの硫黄化合物を除去するための吸着剤として使用されてきたが、そのカゴ型構造を有するゼオライトが、周囲温度で低い吸着速度を有し、従って、かかる温度での液体の処理にとって実用的ではないことが判明した。 Zeolite materials have been used as adsorbents to remove sulfur compounds such as COS from liquid hydrocarbons, but zeolites with their cage structure have a low adsorption rate at ambient temperatures, and thus such temperatures. Proved impractical for the treatment of liquids in
従って、吸着能力の実質的な損失なく再生することがなお可能な高い吸着特性を有するアルミナ吸着剤を用いて、好ましくは水の不在下でCOSなどの硫黄不純物を含む酸性ガスを液体又はガスから除去するための方法を提供することが非常に望ましい。アルミナ吸着剤を使用して液体又はガスからCOS以外の酸性ガスを最小ppmレベルまで除去することも望ましい。 Thus, using an alumina adsorbent with high adsorption properties that can still be regenerated without substantial loss of adsorption capacity, an acidic gas containing sulfur impurities such as COS, preferably in the absence of water, from a liquid or gas It would be highly desirable to provide a method for removal. It is also desirable to use an alumina adsorbent to remove acid gases other than COS from liquids or gases to a minimum ppm level.
Liuによる米国特許第4,835,338号明細書は、活性アルミナ吸着剤を含む吸着媒体に吸着させ、続いて、吸着容量に達した後に活性アルミナを再生させることによる液体炭化水素から硫化カルボニルを除去するための改善された方法を提供する。活性アルミナ吸着剤は、1種以上のアルカリ金属化合物、1種以上のアルカリ土類金属化合物、又はかかる化合物の任意の2種以上の混合物からなるクラスから選択される化合物で前処理され;その後、炭化水素から硫化カルボニルを吸着するために使用され;そして吸着剤にガスを通すことによって再生される。有用な活性アルミナは、1/4インチ〜100メッシュ(150ミクロン)の粒径範囲を有する市販品として開示されている。実際に、アルミナ粒子は、5ミクロンのアルミナ粉末を、吸着プロセスに適したより大きな粒子に凝集することによって形成される。 U.S. Pat. No. 4,835,338 to Liu adsorbs carbonyl sulfide from liquid hydrocarbons by adsorption onto an adsorption medium containing activated alumina adsorbent followed by regeneration of activated alumina after reaching the adsorption capacity. An improved method for removing is provided. The activated alumina adsorbent is pretreated with a compound selected from the class consisting of one or more alkali metal compounds, one or more alkaline earth metal compounds, or a mixture of any two or more of such compounds; Used to adsorb carbonyl sulfide from hydrocarbons; and regenerated by passing gas through the adsorbent. Useful activated alumina is disclosed as a commercial product having a particle size range of 1/4 inch to 100 mesh (150 microns). In practice, alumina particles are formed by agglomerating 5 micron alumina powder into larger particles suitable for the adsorption process.
発明の概要
本発明の課題は、液体又はガスから酸性ガスを除去するための改善された方法であって、1種以上のアルカリ金属化合物、1種以上のアルカリ土類金属化合物、又はそれらの混合物で予め処理した活性アルミナを含む吸着媒体上で酸性ガスを吸着することを含む、前記方法を提供することである。アルミナ吸着剤が、凝集したアルミナ粉末から形成され、且つアルカリ金属及び/又はアルカリ土類金属化合物で処理した後に500オングストロームを超える細孔の少なくとも0.10cc/gの水銀細孔容積をもたらす場合、酸性ガスのために改良された吸着容量が達成されることが判明した。
SUMMARY OF THE INVENTION An object of the present invention is an improved method for removing acidic gases from a liquid or gas, the one or more alkali metal compounds, one or more alkaline earth metal compounds, or mixtures thereof. And adsorbing an acid gas on an adsorption medium comprising activated alumina pretreated in step 1. If the alumina adsorbent is formed from agglomerated alumina powder and results in a mercury pore volume of at least 0.10 cc / g of pores greater than 500 angstroms after treatment with alkali metal and / or alkaline earth metal compound, It has been found that improved adsorption capacity is achieved for acid gases.
発明の詳細な説明
本発明は、活性アルミナ吸着剤上への吸着により、硫化カルボニル(COS)を含む上記のような酸性ガスを液体又はガスから除去するための改善された方法を含む。吸着剤の再生は、吸着剤の容量に達した時に達成され、実施され得る。本発明の方法において使用される活性アルミナ吸着剤は、約1/4インチから約100メッシュ(米国シリーズ)までの粒径範囲を有する活性粒状アルミナを含む。これらの粒子は、約1〜10ミクロンの平均サイズを有する凝集したアルミナ粉末から形成されている。アルミナ粒子は、少なくとも0.45cc/g、通常、少なくとも0.50cc/g、好ましくは少なくとも0.60cc/g、更に好ましくは少なくとも0.70cc/gの全水銀細孔容積で形成される。
DETAILED DESCRIPTION OF THE INVENTION The present invention includes an improved method for removing acid gases such as those described above, including carbonyl sulfide (COS), from liquids or gases by adsorption onto activated alumina adsorbents. Regeneration of the adsorbent can be accomplished and performed when the capacity of the adsorbent is reached. The activated alumina adsorbent used in the process of the present invention comprises activated particulate alumina having a particle size range from about 1/4 inch to about 100 mesh (US series). These particles are formed from agglomerated alumina powder having an average size of about 1 to 10 microns. The alumina particles are formed with a total mercury pore volume of at least 0.45 cc / g, usually at least 0.50 cc / g, preferably at least 0.60 cc / g, more preferably at least 0.70 cc / g.
アルミナ粒子の所望の細孔容積は、約1〜4ミクロンの平均サイズ範囲を有するアルミナ粉末の凝集を含む、幾つかの方法によって達成され得る。より大きなアルミナ粉末、例えば、4ミクロン超が使用される場合、バーンアウト添加剤は粉末で凝集され得る。バーンアウト添加剤は、その後の焼成の間に除去及び/又は炭化される。 The desired pore volume of the alumina particles can be achieved by several methods, including agglomeration of alumina powder having an average size range of about 1-4 microns. If a larger alumina powder is used, eg, greater than 4 microns, the burnout additive can be agglomerated with the powder. The burnout additive is removed and / or carbonized during subsequent firing.
本発明の実施に適した出発材料としては、擬ベーマイト、ギブサイト、バイヤライト及び任意の他の形のアルミナが挙げられ、これらは適切に処理される時に、0.10〜2.5質量%の酸化ナトリウム濃度(1100℃の焼成ベース)、2.0〜9.0質量%のLOI(400℃〜1100℃の加熱によって決定されるヒドロキシル含有率)、及び100〜500m2/gの表面積(BET)を有する吸着剤をもたらす。 Suitable starting materials for the practice of the present invention include pseudoboehmite, gibbsite, bayerite, and any other form of alumina, which, when properly processed, is 0.10-2.5% by weight. Sodium oxide concentration (calculated base at 1100 ° C.), LOI of 2.0-9.0% by weight (hydroxyl content determined by heating at 400 ° C.-1100 ° C.), and surface area of 100-500 m 2 / g (BET Is obtained.
本発明の出発物質は、75ミクロン以上の粒径を有する粒子を有し得る。これらの粒子は、特に有利な吸着を達成するために、約1〜10ミクロンの粒径に粉砕されるべきである。当業者に公知の任意の粉砕技術が使用されてよい。 The starting material of the present invention may have particles having a particle size of 75 microns or more. These particles should be ground to a particle size of about 1-10 microns to achieve a particularly advantageous adsorption. Any grinding technique known to those skilled in the art may be used.
アルミナ出発物質が、約1〜10ミクロンの平均粒径を有するとすぐに、アルミナは高温に短時間曝すことによって急速に活性化される。このような急速な活性化の方法は、当該技術分野で周知である。特に有用であることが見出されている技術の1つは、米国特許第2,915,365号明細書に記載されているものである。この特許取得済みの開示によれば、アルミナは、300℃を上回るガス温度、例えば、300℃〜1000℃で、高温に加熱されたガス(例えば、空気)の流れに注入される。アルミナと高温ガスとの接触の持続時間は、1分未満、例えば、数分の1秒〜数秒であってよく、2秒〜3秒が好ましい接触時間である。一度活性されたアルミナは、ガンマ相又はアモルファス相又はそれらの混合物のいずれかである。 As soon as the alumina starting material has an average particle size of about 1-10 microns, the alumina is rapidly activated by brief exposure to high temperatures. Such rapid activation methods are well known in the art. One technique that has been found to be particularly useful is that described in US Pat. No. 2,915,365. According to this patented disclosure, alumina is injected into a stream of gas (eg, air) heated to a high temperature at a gas temperature above 300 ° C., eg, 300 ° C. to 1000 ° C. The duration of contact between the alumina and the hot gas may be less than 1 minute, such as a fraction of a second to a few seconds, with a preferred contact time being 2 seconds to 3 seconds. Once activated, the alumina is either the gamma phase or the amorphous phase or a mixture thereof.
本発明の好ましい実施態様では、急速に活性されたアルミナは、水の存在下で形成(凝集)したボールであり、その後、当業者に公知の多くの方法のいずれかによって再活性化される。優れた活性アルミナをもたらす方法の1つは、熟成アルミナを300℃〜800℃の範囲の温度に10分〜約4時間にわたり曝すことであり、その際、15分〜2時間、350℃〜450℃の温度が典型的な条件である。粉末活性化のような適切な最終活性化は、低LOIであるが高表面積を有する吸着剤を開発する上で重要である。 In a preferred embodiment of the invention, the rapidly activated alumina is a ball formed (agglomerated) in the presence of water and then reactivated by any of a number of methods known to those skilled in the art. One way to provide excellent activated alumina is to expose the aged alumina to a temperature in the range of 300 ° C. to 800 ° C. for 10 minutes to about 4 hours, with 15 minutes to 2 hours at 350 ° C. to 450 hours. A temperature of ° C is a typical condition. Appropriate final activation, such as powder activation, is important in developing adsorbents with low LOI but high surface area.
一般的には、バーンアウト添加剤は、炭素系材料である。バーンアウト添加剤の例としては、糖、デンプン、及びリグニン又は微粒子粉、例えば、木材、コムギ、トウモロコシ、ライ麦等が挙げられる。ポリエチレンオキシド、ポリビニルアルコール等の水溶性ポリマーを使用することもできる。 Generally, the burnout additive is a carbon-based material. Examples of burnout additives include sugar, starch, and lignin or fine particle powders such as wood, wheat, corn, rye and the like. Water-soluble polymers such as polyethylene oxide and polyvinyl alcohol can also be used.
活性アルミナは、好ましくは、約0.01〜約15質量%、好ましくは約1.0〜約8.0質量%、更に好ましくは約2.0〜約8.0質量%、最も好ましくは約3.0〜約6.0質量%の範囲の量で、1種以上のアルカリ金属化合物、1種以上のアルカリ土類金属化合物、又はそれらの混合物で含浸され、その際、質量%は、含浸されたアルミナ吸着剤の全質量に対する酸化物としての含浸アルカリ金属又はアルカリ土類金属の質量パーセンテージとして測定されている。アルカリ金属化合物又はアルカリ土類金属化合物は、好ましくは、望ましくない他の材料が含浸後にアルミナに残らないように分解性アニオンを有する材料を含む。かかるアルカリ金属/アルカリ土類金属化合物の例としては、例えば、ナトリウム、カリウム、リチウム、カルシウム、及びマグネシウムの水酸化物、炭酸塩、及び硝酸塩が挙げられる。 The activated alumina is preferably about 0.01 to about 15% by weight, preferably about 1.0 to about 8.0% by weight, more preferably about 2.0 to about 8.0% by weight, most preferably about Impregnated with one or more alkali metal compounds, one or more alkaline earth metal compounds, or mixtures thereof in an amount ranging from 3.0 to about 6.0% by weight, wherein the weight percent is impregnated. Measured as a mass percentage of impregnated alkali metal or alkaline earth metal as oxide to the total mass of the alumina adsorbent made. The alkali metal compound or alkaline earth metal compound preferably comprises a material having a degradable anion so that no other undesirable material remains on the alumina after impregnation. Examples of such alkali metal / alkaline earth metal compounds include sodium, potassium, lithium, calcium, and magnesium hydroxides, carbonates, and nitrates.
活性アルミナは、活性アルミナを、溶解したアルカリ金属/アルカリ土類金属化合物を含有する水溶液に少なくとも約5分〜1時間以上にわたり浸漬し、その後、含浸されたアルミナを乾燥させ、300℃〜450℃で1時間〜2時間にわたり再活性化することによってアルカリ金属/アルカリ土類金属化合物によって含浸され得る。必要であれば、複数の含浸及び乾燥のサイクルが使用されてよい。必要であれば、化合物は、噴霧等によって活性アルミナに適用されてもよい。 The activated alumina is soaked in an aqueous solution containing the dissolved alkali metal / alkaline earth metal compound for at least about 5 minutes to 1 hour or more, and then the impregnated alumina is dried to 300 ° C. to 450 ° C. Can be impregnated with an alkali metal / alkaline earth metal compound by reactivation for 1 to 2 hours. If necessary, multiple impregnation and drying cycles may be used. If necessary, the compound may be applied to the activated alumina, such as by spraying.
含浸及び再活性されたアルミナ吸着剤は、処理された吸着剤が、少なくとも0.4cc/g、典型的には少なくとも0.45cc/g、好ましくは少なくとも0.5cc/g、更に好ましくは少なくとも0.55cc/gの全水銀細孔容積を有する場合に改善される。更には、酸ガスの大幅に改善された吸着は、含浸及び再活性化されたアルミナ吸着剤が、少なくとも0.1cc/g、典型的には少なくとも0.15cc/g、好ましくは少なくとも0.30cc/g、更に好ましくは少なくとも0.40cc/gの500オングストロームを上回る細孔の細孔容積を有する場合に達成される。 The impregnated and reactivated alumina adsorbent has a treated adsorbent of at least 0.4 cc / g, typically at least 0.45 cc / g, preferably at least 0.5 cc / g, more preferably at least 0. Improved when having total mercury pore volume of .55 cc / g. Furthermore, greatly improved adsorption of acid gas is achieved when the impregnated and reactivated alumina adsorbent is at least 0.1 cc / g, typically at least 0.15 cc / g, preferably at least 0.30 cc. / G, more preferably at least having a pore volume of more than 500 Angstroms of 0.40 cc / g.
改善された活性アルミナ吸着剤は、ガス又は液体を処理し、最大200ppmの不純物濃度の酸性ガスを含有し且つ1ppm未満まで濃度を低下させることが可能である。このような不純物をその中に含有する液体又はガスからのCOS又は他の酸性ガスの除去は、主として吸着を介して行われるので、特定量の水分の存在又は不在はプロセスの動作にとって重要ではない。しかしながら、酸性ガスの吸着剤の容量は、存在する水の量に反比例して変化することが分かっているので、可能な限り少量の存在する水を用いて動作することが好ましい。また、吸着プロセスが正常に動作するために水が存在する必要がないことに留意すべきである。 The improved activated alumina adsorbent can treat a gas or liquid, contain an acidic gas with an impurity concentration of up to 200 ppm and reduce the concentration to less than 1 ppm. Since the removal of COS or other acidic gases from liquids or gases containing such impurities therein is mainly done through adsorption, the presence or absence of a specific amount of moisture is not critical to the operation of the process. . However, since it has been found that the capacity of the acid gas adsorbent varies inversely with the amount of water present, it is preferable to operate with as little water as possible. It should also be noted that water does not need to be present for the adsorption process to work properly.
好ましい実施態様において、酸性ガスの不純物は、液体又はガス状炭化水素流から除去される。精製されるべき炭化水素流は、上記の吸着容量の低下を避けるために炭化水素流を吸着剤に通す前に存在する水分の全てとは言わなくとも殆どを除去するために、最初に分子篩い又はシリカ等の乾燥床に通されてよい。本発明の吸着剤によって除去されるべき汚染物質は、COS、H2S、CO2、CS2、SO2、HCl、HF、HBrを含む液体中に溶解した酸性ガスであり、その際、この流れの主成分は主にエチレン、プロピレン、ブタン、又は種々のオレフィン類の混合物、天然ガス、バイオマス由来の合成ガス、水素、窒素、又は空気からなる。この流れの主成分は、ガス又は液体のいずれかの形であってよい。 In a preferred embodiment, acid gas impurities are removed from the liquid or gaseous hydrocarbon stream. The hydrocarbon stream to be purified is first screened to remove most if not all of the water present prior to passing the hydrocarbon stream through the adsorbent to avoid the aforementioned reduction in adsorption capacity. Alternatively, it may be passed through a dry bed such as silica. The pollutant to be removed by the adsorbent of the present invention is an acid gas dissolved in a liquid containing COS, H 2 S, CO 2 , CS 2 , SO 2 , HCl, HF, HBr. The main components of the stream consist mainly of ethylene, propylene, butane or a mixture of various olefins, natural gas, biomass-derived synthesis gas, hydrogen, nitrogen or air. The main component of this stream may be in either gas or liquid form.
水分が炭化水素流中に存在する場合、酸性ガスの一部は、加水分解により他の反応生成物に変換されてよく、これらはその後、アルカリ金属を含浸させた活性アルミナ吸着剤に吸着されてよい。このような吸着された反応生成物は、その後、必要であれば、吸着剤の次の再生時に、吸着された酸性ガスと一緒に除去されてよい。 When moisture is present in the hydrocarbon stream, some of the acid gas may be converted to other reaction products by hydrolysis, which are then adsorbed on an activated alumina adsorbent impregnated with alkali metal. Good. Such adsorbed reaction product may then be removed along with the adsorbed acid gas during subsequent regeneration of the adsorbent, if necessary.
吸着プロセスは、都合が良ければ15℃〜100℃の温度が使用されてよいが、周囲温度で実施されてよく、例えば、汚染液体又はガスが前の処理からこの温度である場合、吸着剤を通る前に、加熱又は冷却される必要がない。 The adsorption process may be carried out at a temperature between 15 ° C. and 100 ° C. if convenient, but may be carried out at ambient temperature, for example if the contaminating liquid or gas is at this temperature from the previous treatment, the adsorbent is removed. There is no need to be heated or cooled before passing.
吸着剤と酸性ガス汚染フィードとの間の接触を維持する他の任意の都合の良い形態が、例えば、スラリープロセスとして利用されてもよいが、吸着は、有利には充填塔で行われてよい。吸着剤を通したフィードの流量は、アルカリ金属/アルカリ土類金属含浸活性アルミナ上へのフィードからの酸性ガスの所望の吸着が起こるのに十分な接触時間を可能にするために十分に遅くなければならない。実際の接触時間の量は、吸着剤の粒径によって変化する。 Any other convenient form of maintaining contact between the adsorbent and the acid gas contaminated feed may be utilized, for example as a slurry process, but the adsorption may advantageously be performed in a packed column. . The feed flow rate through the adsorbent should be slow enough to allow sufficient contact time for the desired adsorption of acid gas from the feed onto the alkali metal / alkaline earth impregnated activated alumina to occur. I must. The actual amount of contact time will vary with the particle size of the adsorbent.
硫黄含有酸性ガスのアルカリ金属/アルカリ土類金属含浸活性アルミナ吸着剤の吸着容量は、吸着剤からの流出物の硫黄含有率を監視することによって決定される。その吸着容量に達する前に、流出物は1ppm未満の硫黄を含有する。吸着剤の容量に達したことを示すこのような監視後、即ち、流出物の硫黄含有量の増加により、吸着剤は、空気、炭化水素ガス、窒素又は他の不活性ガスなどの加熱ガスを吸着剤に通すことによって再生され得る。加熱されたガスは、好ましくは、その上に吸着された相当量の硫黄が除去されるまで、好ましくは約100℃〜300℃、更に好ましくは約150℃〜250℃、最も好ましくは約250℃までの温度に加熱され且つ約1〜10cc/分の速度で吸着剤に通される。相当量は、吸着された硫黄の約40質量%以上である。これは、吸着剤中の残留硫黄の量を分析することによって容易に決定され得る。吸着剤を通る再生ガスの流れの方向が、例えば、吸着剤が塔に充填される時に、フィード流と同じ方向であるか、又は再生ガスが、通常のフィードの流れに対して反対の方向に吸着剤を通るかいずれかである。他の酸性ガスの吸着容量は、他の陰イオン種、例えば、Cl、F等を測定するための公知の手段によって決定され得る。 The adsorption capacity of an alkali metal / alkaline earth metal impregnated activated alumina adsorbent of sulfur-containing acid gas is determined by monitoring the sulfur content of the effluent from the adsorbent. Before reaching its adsorption capacity, the effluent contains less than 1 ppm sulfur. After such monitoring to indicate that the capacity of the adsorbent has been reached, i.e., due to an increase in the sulfur content of the effluent, the adsorbent is heated with a heated gas such as air, hydrocarbon gas, nitrogen or other inert gas. It can be regenerated by passing it through an adsorbent. The heated gas is preferably about 100 ° C. to 300 ° C., more preferably about 150 ° C. to 250 ° C., and most preferably about 250 ° C. until a substantial amount of sulfur adsorbed thereon is removed. And is passed through the adsorbent at a rate of about 1 to 10 cc / min. A substantial amount is about 40% by weight or more of the adsorbed sulfur. This can be easily determined by analyzing the amount of residual sulfur in the adsorbent. The direction of the regeneration gas flow through the adsorbent is, for example, the same direction as the feed stream when the adsorbent is packed into the column, or the regeneration gas is in the opposite direction to the normal feed flow Either through the adsorbent. The adsorption capacity of other acid gases can be determined by known means for measuring other anionic species such as Cl, F, and the like.
以下の実施例は、本発明の方法をより良く例示する役割を果たす。 The following examples serve to better illustrate the method of the present invention.
実施例
COS吸着剤を、下記の通り製造した。吸着剤をそれぞれの床に置き、下記のように急速老化の試験条件に曝し、破過試験を行った。
Examples COS adsorbents were prepared as follows. The adsorbent was placed on each floor and exposed to the test conditions for rapid aging as described below, and a breakthrough test was conducted.
試験条件
急速な老化(高速再生)
各床には、78グラムの吸着剤を装填した。吸着剤床を、その後、吸着、再生及び冷却のサイクルに供した。3つの工程を合計35回繰り返した。35サイクルの最後に、各床を270℃で0.5slpmの流れで更に2時間加熱し、次いで周囲温度に冷却した。急速な老化の吸着工程の間に、窒素中の450ppmのCOSを、8.7slpmの流量、35℃の温度及び80psi(絶対)の圧力で35分間、床に供給した。再生工程の間、床は、吸着工程に対して向流の0.5slpmの窒素供給の流れで、15psi(絶対)の圧力及び270℃の温度であった。急速な老化の冷却工程の間、床は、吸着工程に対して向流の0.5slpmの窒素供給の流れで、15psi(絶対)の圧力及び35℃の温度であった。
Test conditions Rapid aging (high-speed regeneration)
Each bed was loaded with 78 grams of adsorbent. The adsorbent bed was then subjected to an adsorption, regeneration and cooling cycle. The three steps were repeated a total of 35 times. At the end of the 35 cycles, each bed was heated at 270 ° C. with a flow of 0.5 slpm for an additional 2 hours and then cooled to ambient temperature. During the rapid aging adsorption process, 450 ppm COS in nitrogen was fed to the bed for 35 minutes at a flow rate of 8.7 slpm, a temperature of 35 ° C. and a pressure of 80 psi (absolute). During the regeneration process, the bed was at a pressure of 15 psi (absolute) and a temperature of 270 ° C. with a flow of 0.5 slpm nitrogen feed countercurrent to the adsorption process. During the rapid aging cooling step, the bed was at a pressure of 15 psi (absolute) and a temperature of 35 ° C. with a flow of 0.5 slpm nitrogen feed countercurrent to the adsorption step.
破過試験
床が急速な老化試験を完了した後、破過試験を完了した。この試験の間、窒素中の75ppmのCOSを、6.45slpmの流量及び35℃の温度で床に供給した。床を、COSが床の出口で供給条件に達するような時間にわたり運転した。
Breakthrough test The breakthrough test was completed after the bed completed a rapid aging test. During this test, 75 ppm COS in nitrogen was fed to the bed at a flow rate of 6.45 slpm and a temperature of 35 ° C. The bed was operated for a time such that the COS reached the feed conditions at the bed outlet.
実施例1
ビーズを、15グラムの細孔形成剤と、85グラムの約5ミクロンの大きさのフラッシュ焼成アルミナ粉末とを混合して調製した。材料を、パンアグロメレーション技術を使用してビーズに形成し、7×14タイラーメッシュにスクリーニングした。材料を、その後、842°Fの温度で2時間焼成した。活性化された材料を、その後、9.8質量%のNaOH溶液中に20分間浸漬し、その材料を再び572°Fの温度及び2時間にわたり活性化した。得られた材料は、6質量%のNa2O含有率を有していた。
Example 1
Beads were prepared by mixing 15 grams of pore former and 85 grams of flash calcined alumina powder about 5 microns in size. The material was formed into beads using a pan agglomeration technique and screened to a 7 × 14 Tyler mesh. The material was then fired at a temperature of 842 ° F. for 2 hours. The activated material was then immersed in a 9.8 wt% NaOH solution for 20 minutes, and the material was again activated at a temperature of 572 ° F. for 2 hours. The resulting material had a Na 2 O content of 6% by weight.
実施例2
実施例1からの材料を、急速老化プロトコルに記載されているように急速に老化した。老化後、実施例1からの材料を、次に、破過試験で試験した。材料を、640分以内に2ppmのCOSに破過し、880分以内に25ppmのCOSに破過した。
Example 2
The material from Example 1 was rapidly aged as described in the rapid aging protocol. After aging, the material from Example 1 was then tested in a breakthrough test. The material broke through to 2 ppm COS within 640 minutes and into 25 ppm COS within 880 minutes.
実施例3
ビーズを、約5ミクロンのアルミナ粉末を、約1.5ミクロンの粉末に粉砕することにより調製した。アルミナ粉末を、パンアグロメレーション技術を使用してビーズに形成し、7×14タイラーメッシュにスクリーニングした。ビーズを、その後、700°Fの温度で2時間にわたり焼成した。活性化ビーズを、その後、9.8質量%のNaOH溶液中に20分間浸漬し、ビーズを再び572°Fの温度で2時間にわたりパン活性剤で活性化した。得られた材料は、6質量%のNa2O含有率を有していた。
Example 3
The beads were prepared by grinding about 5 micron alumina powder to about 1.5 micron powder. Alumina powder was formed into beads using a pan agglomeration technique and screened to a 7 × 14 Tyler mesh. The beads were then fired for 2 hours at a temperature of 700 ° F. The activated beads were then immersed in a 9.8 wt% NaOH solution for 20 minutes and the beads were again activated with bread activator for 2 hours at a temperature of 572 ° F. The resulting material had a Na 2 O content of 6% by weight.
実施例4
実施例3からの材料を、急速老化プロトコルに記載されているように急速に老化した。老化後、実施例3からの材料を、次に、破過試験で試験した。材料を640分以内に2ppmのCOSに破過し、880分以内に25ppmのCOSに破過した。
Example 4
The material from Example 3 rapidly aged as described in the rapid aging protocol. After aging, the material from Example 3 was then tested in a breakthrough test. The material broke through to 2 ppm COS within 640 minutes and to 25 ppm COS within 880 minutes.
実施例5(対照)
ビーズを、約5ミクロンのアルミナ粉末をフラッシュ活性化し、その後、活性化した粉末を、パンアグロメレーション技術を用いてビーズに形成することによって調製した。ビーズを7×14タイラーメッシュにスクリーニングした。材料を、その後、760°Fの温度で2時間にわたり焼成した。活性化した材料を、その後、9.8質量%のNaOH溶液中に20分間浸漬し、材料を再び572°Fの温度で2時間にわたりパン活性剤で活性化した。得られた材料は、4質量%のNa2O含有率を有していた。
Example 5 (control)
The beads were prepared by flash activating about 5 micron alumina powder, after which the activated powder was formed into beads using a pan agglomeration technique. The beads were screened on a 7 × 14 Tyler mesh. The material was then fired at a temperature of 760 ° F. for 2 hours. The activated material was then immersed in a 9.8 wt% NaOH solution for 20 minutes and the material was again activated with bread activator at a temperature of 572 ° F. for 2 hours. The resulting material had a Na 2 O content of 4% by weight.
実施例6(対照の結果)
実施例5からの対照材料を、急速老化プロトコルに記載されているように急速に老化させた。これを、その後、破過試験で試験した。対照の材料は、250分以内に2ppmのCOSに破過し、497分以内に25ppmのCOSに破過した。
Example 6 (control results)
The control material from Example 5 was rapidly aged as described in the rapid aging protocol. This was then tested in a breakthrough test. The control material broke through to 2 ppm COS within 250 minutes and into 25 ppm COS within 497 minutes.
実施例7(対照)
ビーズを、約5ミクロンのアルミナ粉末をフラッシュ活性化し、その後、パンアグロメレーション技術を用いてビーズに形成することによって調製した。ビーズを7×14メッシュにスクリーニングした。材料を、その後、760°Fの温度で2時間にわたり焼成した。活性化した材料を、その後、12質量%のNaOH溶液中に20分間浸漬し、材料を再び572°Fの温度で2時間にわたり活性化した。得られた材料は、6質量%のNa2O含有率を有していた。
Example 7 (control)
The beads were prepared by flash activating about 5 micron alumina powder and then forming into beads using a pan agglomeration technique. The beads were screened to 7x14 mesh. The material was then fired at a temperature of 760 ° F. for 2 hours. The activated material was then immersed in a 12 wt% NaOH solution for 20 minutes and the material was again activated for 2 hours at a temperature of 572 ° F. The resulting material had a Na 2 O content of 6% by weight.
実施例8(対照の結果)
実施例7からの対照材料を、急速老化プロトコルに記載されているように急速に老化させ、その後、破過試験で試験した。材料を300分以内に2ppmのCOSに破過し、500分以内に25ppmのCOSに破過した。
Example 8 (control results)
The control material from Example 7 was rapidly aged as described in the rapid aging protocol and then tested in a breakthrough test. The material broke through to 2 ppm COS within 300 minutes and to 25 ppm COS within 500 minutes.
実施例9
実施例1からの材料の細孔容積を、浸漬する前に、マイクロメリティックス社製の機器を使用して水銀細孔対称性により測定した。材料の全細孔容積は0.63cc/gであった。500オングストロームより大きい細孔の細孔容積は0.61cc/gであった。
Example 9
The pore volume of the material from Example 1 was measured by mercury pore symmetry using a Micromeritics instrument before soaking. The total pore volume of the material was 0.63 cc / g. The pore volume of pores larger than 500 angstroms was 0.61 cc / g.
実施例10
実施例3からの材料の細孔容積を、浸漬する前に、マイクロメリティックス社製の機器を使用して水銀細孔対称性により測定した。材料の全細孔容積は0.72cc/gであった。500オングストロームより大きい細孔の細孔容積は0.29cc/gであった。
Example 10
The pore volume of the material from Example 3 was measured by mercury pore symmetry using a Micromeritics instrument before soaking. The total pore volume of the material was 0.72 cc / g. The pore volume of pores larger than 500 angstroms was 0.29 cc / g.
実施例11
実施例5及び7からの対照材料の細孔容積を、浸漬する前に、マイクロメリティックス社製の機器を使用して水銀細孔対称性により測定した。それぞれの材料の全細孔容積は0.38cc/gであった。500オングストロームより大きい細孔の細孔容積は0.11cc/gであった。
Example 11
The pore volume of the control material from Examples 5 and 7 was measured by mercury pore symmetry using a Micromeritics instrument before soaking. The total pore volume of each material was 0.38 cc / g. The pore volume of pores larger than 500 angstroms was 0.11 cc / g.
表1は上記の試験の結果をまとめる。
実施例12
実施例1、3、5及び7の材料を、浸漬及び活性化後に細孔容積について測定した。浸漬及び活性化後の実施例1の材料は、0.56g/ccの全細孔容積を有し、500オングストロームより大きい細孔の場合、0.15g/ccの細孔容積を有していた。浸漬及び活性化後の実施例3の材料は、0.59g/ccの全細孔容積を有し、500オングストロームより大きい細孔の場合、0.41g/ccの細孔容積を有していた。浸漬及び活性化後の対照例5の材料は、0.36g/ccの全細孔容積を有し、500オングストロームより大きい細孔の場合、0.07g/ccの細孔容積を有していた。浸漬及び活性化後の対照例7の材料は、0.34g/ccの全細孔容積を有し、500オングストロームより大きい細孔の場合、0.04g/ccの細孔容積を有していた。
The materials of Examples 1, 3, 5 and 7 were measured for pore volume after immersion and activation. The material of Example 1 after soaking and activation had a total pore volume of 0.56 g / cc, and for pores larger than 500 angstroms, it had a pore volume of 0.15 g / cc. . The material of Example 3 after soaking and activation had a total pore volume of 0.59 g / cc and a pore volume of 0.41 g / cc for pores larger than 500 angstroms. . The Control 5 material after soaking and activation had a total pore volume of 0.36 g / cc, and a pore volume of 0.07 g / cc for pores greater than 500 angstroms. . Control 7 material after soaking and activation had a total pore volume of 0.34 g / cc, and 0.04 g / cc pore volume for pores greater than 500 angstroms. .
Claims (19)
液体又はガスの酸性ガス汚染物質の含有率を低下させるのに十分な時間にわたり液体又はガス中の酸性ガス汚染物質を吸着するために、酸性ガス汚染物質を含有する液体又はガスと、1.0〜8.0質量%の金属化合物で含浸された活性アルミナ吸着剤(前記質量比は、含浸された活性アルミナ吸着剤に対する金属化合物中の酸化物としての金属の質量比を基準とする)とを接触させる工程を含み、前記金属化合物は1種以上のアルカリ金属化合物、1種以上のアルカリ土類金属化合物、又はかかる化合物の混合物からなる群から選択され、その際、前記含浸されたアルミナ吸着剤は、少なくとも0.10cc/gの500オングストロームを超える細孔の水銀細孔容積を有し、前記液体又はガスが炭化水素流であるオレフィン流又は天然ガス流であり、かつ、前記酸性ガスがCOS、H 2 S、CS 2 又はSO 2 である、前記方法。 A method of removing acid gas pollutants from a liquid or gas by adsorption,
A liquid or gas containing an acid gas contaminant to adsorb the acid gas contaminant in the liquid or gas for a time sufficient to reduce the content of the acid gas contaminant in the liquid or gas; 1.0 Activated alumina adsorbent impregnated with ~ 8.0 wt% metal compound (the mass ratio is based on the mass ratio of the metal as an oxide in the metal compound to the impregnated active alumina adsorbent) Including the step of contacting, wherein the metal compound is selected from the group consisting of one or more alkali metal compounds, one or more alkaline earth metal compounds, or a mixture of such compounds, wherein the impregnated alumina adsorbent may have a mercury pore volume of pores exceeding 500 Å of at least 0.10 cc / g, olefin stream or natural gas the liquid or gas is a hydrocarbon stream A scan stream, and wherein the acidic gas is COS, H 2 S, CS 2 or SO 2, said method.
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